CN103154285B - Copper alloy hot-forged part and process for producing copper alloy hot-forged part - Google Patents

Copper alloy hot-forged part and process for producing copper alloy hot-forged part Download PDF

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CN103154285B
CN103154285B CN201180048837.8A CN201180048837A CN103154285B CN 103154285 B CN103154285 B CN 103154285B CN 201180048837 A CN201180048837 A CN 201180048837A CN 103154285 B CN103154285 B CN 103154285B
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forging
hot
mass
cooling
endurance
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CN103154285A (en
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大石惠一郎
积川靖弘
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Mitsubishi Shindoh Co Ltd
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Mitsubishi Shindoh Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Forging (AREA)

Abstract

This copper alloy hot-forged part has an alloy composition which contains 0.21 to 0.44 mass% of Co, 0.06 to 0.13 mass% of P, 0.003 to 0.08 mass% of Sn and 0.00003 to 0.0030 mass% of O, with the balance consisting of Cu and unavoidable impurities, and in which the Co content, [Co] mass%, and the P content, [P] mass%, satisfy the relationship: 3.1 = ([Co] - 0.005)/([P] - 0.006) = 4.9. In the cross-sectional metal structure, the sum of the fraction of recrystallized-grain groups where the recrystallized grains have an average grain diameter of 0.050 to 0.50mm and the fraction of un-recrystallized grains is 80% or above.

Description

The manufacture method of copper alloy hot forging and copper alloy hot forging
Technical field
The present invention relates to the manufacture method of an Albatra metal-hot forging and copper alloy hot forging.Relate in particular to the manufacture method of copper alloy hot forging and the copper alloy hot forging thereof of a kind of intensity, endurance, heat conductivity, electrical conductivity and creep properties excellence.
Background technology
Heat conductivity and electrical conductivity that copper performance is higher, can be used for the various industrial fields such as radiator element, scatterer, short-circuited conducting sleeve, terminal, base, junctor, electrode, sensor module, model, pressurized vessel.Yet, take the so-called fine copper with more than 99.9% copper concentration that tough pitch copper, oxygen free copper and phosphorized copper be representative because intensity is lower, so the copper of per unit area is used the many and cost of quantitative change to uprise in order to ensure intensity, it is large that volume and weight also become.
And, along with semiconductor element highly integrated/high capacity, the height output controller for motor that is used in automobile is required also effectively to emit by the surface-area of the whole radiator element of the expansions such as fan portion or scatterer the hot higher heat conductivity producing in semi-conductor with semiconductor element etc. and for emitting hot radiator element or the scatterer that semi-conductor produces.
In addition, about radiator element etc., in order to emit more heat, can consider that by water-cooling pattern, further improving its efficiency uses, but now, need watertight intensity, especially need initial deformation intensity, endurance is larger.And these radiator element need excellent exothermicity, but need to make intensity or hardness can be because of assembling procedure time or the temperature when welding that is applied in during encapsulation or brazing declines.And, even if need in use temperature rising also can bear the higher creep properties of its temperature.
And, about being used in the short-circuited conducting sleeve of motor, by brazing, undertaken and the engaging of rotor bar, even if also need higher intensity and higher heat conductivity and electrical conductivity after soldering.And, owing in use there is the temperature rising that surpasses 100 ℃, therefore require heat extraction (thermal conduction) property excellent.And, if run at high speed, can produce larger centrifugal force, so requirement can bear the higher intensity of its centrifugal force, surpass the higher creep properties under the environment of 100 ℃.Radiator element or junctor, electrode etc. are also identical, the higher creep properties that requirement is born in can using for a long time continuously.
Like this, to intensity, endurance, heat conductivity, electrical conductivity and creep properties for the copper alloy of purposes is had relatively high expectations as mentioned above.
Working method to above-mentioned radiator element etc. describes, for process as for enlarged surface is long-pending, on surface, be provided with the radiator element of jut, large-scale terminal or junctor, electrode, sensor module complex contour shape or as the short-circuited conducting sleeve of motor be tubular shape, can be by forge hot or cutting, punching press and Cold Forging.Yet machining can become materials processing various shapes, but because the machinability of the higher copper alloy of copper concentration is very poor, so add man-hour requirement extensive work amount, and yield rate is poor, does not therefore have economy.If wish is by punching press or cold-forge forming, copper to process curing, so cannot apply larger degree of finish, and shape that cannot processed complex.For by the shape of punching press or Cold Forging complexity, must after reaching Processing limit, anneal/pickling, and then make complicated shape by punching press and cold forging, so cost is larger.
Therefore, preferably as the method for making composite molding extremely simultaneously in 1 operation, by forge hot, manufacture.If forge hot, even if also can be shaped to complicated shape for the less swaging machine of press capacity, cost is lower.
Yet general copper and the forge hot of copper alloy are generally processed under the high temperature of 700 ℃ or 800 ℃, so the unusual problem of step-down and so on of the intensity that has copper after forge hot and a copper alloy.Therefore, can consider to be used as the Cr-Zr copper (lmass%Cr-0.lmass%Zr-C u) of solution-Precipitation type alloy, rather than general copper and copper alloy.But, this alloy, owing to comprising active element Zr, so dissolve/casting cost is larger, is again heated to material more than 950 ℃ (950～1000 ℃) conventionally after forge hot, at once impose quenching, and manufacture through the thermal treatment process of overaging and so on thereafter.Reheating of 950 ℃ of this high temperature can increase cost, if heat in atmosphere, produces oxidation loss, therefore in complicated shape, also deposits problem dimensionally.And reheating of Yin Gaowen and forging be distortion easily, and produce adhesion between material.Therefore, in rare gas element or vacuum, with 950 ℃, heat-treat, although prevent oxidation loss, cost uprises, and also has distortion or adhesion problems.
And, propose by the copper alloy for forge hot forming (referring to Patent Document 1) that limits Al, Si, Ni etc.
Yet the copper alloy of recording in patent documentation 1 needs special solutionization to process and exist poor and so on the problem of electricity/heat conductivity.
Patent documentation 1: Japanese Patent Publication 2002-80924 communique
Summary of the invention
The present invention completes in order to solve the problem of this prior art, and its problem is to provide the manufacture method of copper alloy hot forging and the copper alloy hot forging of a kind of intensity, endurance, heat conductivity and electrical conductivity excellence.
In order to solve described problem, the inventor etc. are studied the composition of copper alloy or metal structure.Its result, learn following opinion, in the copper alloy of predetermined composition, can be by carry out forge hot under predetermined condition, and the shared ratio of the recrystal grain group in pre-determined range and the shared ratio of non-recrystallization crystal grain are located at and in pre-determined range, obtain the copper alloy hot forging that intensity, endurance, heat conductivity, electrical conductivity etc. are excellent by average crystallite particle diameter.
The inventor of the present invention based on above-mentioned etc. opinion completes., in order to solve described problem, the invention provides an Albatra metal-hot forging, it is characterized in that, described its alloy composition of copper alloy hot forging is the Co that contains 0.21～0.44mass%, the P of 0.06～0.13mass%, 0 of the Sn of 0.003～0.08mass% and 0.00003～0.0030mass%, remainder comprises Cu and inevitable impurity, the relation between content [Co] mass% of Co and content [P] mass% of P with 3.1≤([Co]-0.005)/([P]-0.006)≤4.9, in the metal structure of cross section, adding up to more than 80% of the ratio that the ratio that recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared and non-recrystallization crystal grain are shared.
Non-recrystallization crystal grain described in this specification sheets is described.Recrystal grain before forge hot is subject to strain but is not carried out recrystallize being called non-recrystallization crystal grain to remain the residual crystal grain of state of strain because of forge hot.If whether observation metal structure, remain strain in known crystal grain, recrystal grain and non-recrystallization crystal grain can be observed the residual of strain and identify, but identification as follows in the present invention.If recrystal grain demonstrates the shape of approximate regular hexagon, and describe to be external in crystal grain circumscribed circle and in be connected to the inscribed circle of crystal grain, the ratio of (the external circular diameter of crystal grain)/(diameter of the inscribed circle of crystal grain) of most of recrystal grain is less than 2.0.Therefore by the ratio of (the external circular diameter of crystal grain)/(diameter of the inscribed circle of crystal grain), be, that more than 2.0 crystal grain is made as non-recrystallization crystal grain.Shown in Fig. 1, be external in crystal grain external circular diameter and in be connected to the example of diameter of the inscribed circle of crystal grain.
Then, the average crystallite particle diameter of the recrystal grain group described in this specification sheets and recrystal grain group is described.According to JIS H0501, measure the average crystallite particle diameter of recrystal grain.And, when the metal structure in the visual field that it is observed is recrystal grain, the set of all recrystal grains in its visual field is called to the recrystal grain group in its visual field.And when if the average crystallite particle diameter of the recrystal grain in the observed visual field is made as amm, the recrystal grain in its visual field is made as the recrystal grain group that the average crystallite particle diameter of recrystal grain is amm.Like this, by each visual field of observing, measure the average crystallite particle diameter of recrystal grain group.
And the cross section metal structure described in this specification sheets is made as the metal structure in the part of the part that is 1mm except the case depth apart from forging in cutting off at least one cross section of forging.
Preferably further contain the Zn of 0.001～0.3mass%, any more than a kind in the Ag of the Mg of 0.002～0.2mass%, 0.001～0.3mass%.
According to this preferred copper alloy hot forging, owing to thering is any in Zn, Mg, Ag, so improve intensity.
And, copper alloy hot forging can further contain the Ni of 0.005～0.15mass%, any more than a kind in the Fe of 0.003～0.10mass%, has the relation of 3.1≤([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006)≤4.9 and 0.010≤2 * [Ni]+3 * [Fe]≤0.75 * [Co] between content [Fe] mass% of content [Ni] mass%, Fe of content [Co] mass%, the Ni of Co and content [P] mass% of P.
According to this copper alloy hot forging, even if having any in Ni and Fe, intensity, endurance, heat conductivity, electrical conductivity etc. are also excellent.
Preferably endurance is 230N/mm 2above, the thermal conductivity at 20 ℃ is more than 300W/mK, or the electric conductivity at 20 ℃ is more than 75%IACS, and described endurance is made as to L (N/mm 2), described thermal conductivity is when being made as M (W/mK), described electric conductivity and being made as N (%IACS), the value of (L * M) is more than 77000, or the value of (L * N) is more than 19000.
About endurance, heat conductivity and the electrical conductivity requiring in radiator element, junctor and short-circuited conducting sleeve, the more high saving of more relating to material of their numerical value, and relate to the densification of the finished product.At this, if be that 320～395W/mK, conductivity are that 83～102%IACS, endurance are 40～80N/mm by the thermal conductivity at 20 ℃ of the hot forging of general fine copper (C1020, C1100 and C1220) 2, endurance and thermal conductivity amass be 17000～25000, amassing of endurance and electric conductivity be that the situation of 4500～6000 left and right is taken into account, above-mentioned in preferred numerical value certainly bring into play larger effect.In addition, the endurance of the hot forging of industrial pure is about 30N/mm 2, the thermal conductivity at 20 ℃ is about 220W/mK, electric conductivity is about 60%IACS, far beyond these numerical value.
More preferably endurance is 250N/mm 2above, the thermal conductivity at 20 ℃ is more than 310W/mK, or electric conductivity is more than 77%IACS, and amassing of endurance and thermal conductivity is more than 82000, or amassing of endurance and electric conductivity is more than 20000.Most preferably there is the high thermal conductivity identical with fine copper and high electrical conductivity, the numerical value of endurance aspect for exceeding far away, endurance is 260N/mm 2above, the thermal conductivity at 20 ℃ is more than 320W/mK, or electric conductivity is more than 80%IACS, and amassing of endurance and thermal conductivity is more than 85000, or amassing of endurance and electric conductivity is more than 21000.
And, it is characterized in that, at 200 ℃, apply 50N/mm 2stress, while carrying out creep test, the total creep deflection that does not comprise initial deformation is below 0.05%.As described later, it is characterized in that, if implement 5～20% cold working after forge hot and before separating out thermal treatment, at 200 ℃, apply 100N/mm 2stress and while carrying out the creep test of 1000 hours, the total creep deflection that does not comprise initial deformation is below 0.15%.
The median size of the precipitate in preferred described recrystal grain be 1.3～3.9nm or precipitate more than 90% be 0.7～7nm.
According to this preferred copper alloy hot forging, because the median size of precipitate is 1.3～3.9nm, or precipitate more than 90% become 0.7～7nm, therefore can there is high endurance, high thermal conductivity, high electrical conductivity, and under the environment for use of 100～200 ℃, there is higher creep properties.
The shared ratio of described recrystal grain group that the average crystallite particle diameter of preferred described recrystal grain is 0.050～0.50mm is more than 60%, or the shared ratio of described non-recrystallization crystal grain is more than 60%.
According to this preferred copper alloy hot forging, can under the environment for use of 100～200 ℃, there is higher creep properties.
Preferably at 825 ℃, heated for 300 seconds, cooling endurance is afterwards 125N/mm 2above, the thermal conductivity at described after cooling 20 ℃ is more than 280W/mK, or the electric conductivity at described after cooling 20 ℃ is more than 70%IACS, and described endurance after cooling is made as to L (N/mm 2), the thermal conductivity at described after cooling 20 ℃ is when being made as electric conductivity at M (W/mK), described after cooling 20 ℃ and being made as N (%IACS), the value of (L * M) is more than 38000, or the value of (L * N) is more than 9600.
BAg-5:45Ag-30Cu-25Zn solder alloy, BAg-6:50Ag-34Cu-16Zn solder alloy and the BAg-7:56Ag-22Cu-17Zn-5Sn solder alloy in the JIS Z3261 of for example short-circuited conducting sleeve of producing with hot forging of the present invention working strength or heat conductivity and electrical conductivity excellence when engaging with rotor bar, recorded, its brazing temperature is recommended respectively the high temperature of 745～845 ℃, 775～870 ℃ and 650 ℃～750 ℃.Therefore, although requirement is that the short period of time is as the thermotolerance of 800 ℃ of left and right of brazing temperature to short-circuited conducting sleeve.Certainly, owing to can be used for electric power purposes, so even the heat conductivity of also having relatively high expectations after brazing and electrical conductivity.And, the short-circuited conducting sleeve that is used in motor due to centrifugal force because of high speed larger, so also need to bear its centrifugal intensity of force.
That is, it is characterized in that, in being equivalent to the salt bath of 825 ℃ of Ag soldering condition, this forging is flooded in the material of 300 seconds and heating, endurance is 125N/mm 2above, preferred 130N/mm 2above, the thermal conductivity at 20 ℃ is more than 280W/mK, or electric conductivity is more than 70%IACS, and amassing of endurance and thermal conductivity is more than 38000, or amassing of endurance and electric conductivity is more than 9600.And, it is characterized in that, at 200 ℃, to being equivalent to the heat treated hot forging of brazing, apply 50N/mm 2stress, and while carrying out the creep test of 1000 hours, the total creep deflection that does not comprise initial deformation is below 0.25%.In addition, it is characterized in that about short-circuited conducting sleeve etc., having the hot forging of even surface, implement 5～20% cold working, thereby in the salt bath of 825 ℃, heat in the test film in 300 seconds after forge hot and before separating out thermal treatment, endurance is 150N/mm 2above, the thermal conductivity at 20 ℃ is more than 280W/mK, or electric conductivity is more than 70%IACS, and amassing of endurance and thermal conductivity is more than 48000, or amassing of endurance and electric conductivity is more than 12000.In addition, it is characterized in that, at 200 ℃, to being equivalent to the heat treated hot forging of brazing, apply 50N/mm 2stress, and while carrying out the creep test of 1000 hours, except initial deformation, creep strain amount is below 0.15%.In addition, after air cooling, implement the thermal treatment that is mainly used in recovery heat/conductivity of 30 minutes in the salt bath of 590 ℃ after, measure these characteristic values.Even in implementing the material of these brazing, also there is higher intensity, higher heat conductivity and higher electrical conductivity, so become the hot forging of the radiator element that is suitable for the short-circuited conducting sleeve of high speed rotating most or is subjected to pressure etc.
The suitable part of soldering is because average crystallite particle diameter is 0.05mm, even thick is more than 0.08mm, even if therefore keep being equivalent to the time of soldering under the high temperature of 825 ℃, also can postpone the crystal grain-growth of precipitate, although how many, become large, but contribute to the nano-precipitation of endurance still more, so endurance is higher.By the thermal treatment that makes heat conductivity/electrical conductivity recover after carrying out soldering, be in soldering process of cooling afterwards, the temperature provinces of 650 ℃ to 550 ℃ cooling 5～50 minutes, or temporary transient air cooling after brazing, and keep 5～50 minutes at the temperature of 550 ℃～650 ℃, carry out thus demonstrating good endurance, heat conductivity/electrical conductivity after soldering.Especially after carrying out forge hot, if apply 5～20% cold working, endurance uprises.This be because, the average crystallite particle diameter of hot forging is 0.05mm, more than 0.08mm, even if be therefore heated to 825 ℃, the also residual processing strain importing by cold working, the intensity that is equivalent to its strain is added in together.That is, even hot forging is heated to more than 800 ℃ by soldering, because average crystallite particle diameter is greater than 0.05mm or 0.08mm, so also can postpone the growth of precipitate particle, remain in a large number the precipitate particle that helps endurance, in addition, processing strain is added in together, thereby has 150N/mm 2above higher endurance.About creep strain, hot forging is also larger due to crystal grain, so velocity of diffusion is slower, and owing to thering is thermotolerance, so even if apply higher stress, deflection is also less.Apply cold worked hot forging owing to thering is higher endurance, so creep strain amount is less.In addition, if forging be impregnated in the salt bath of high-temp liquid, the temperature of forging material sharply rises.Therefore,, at the temperature more than 800 ℃ and below 825 ℃, hot forging floods and keeps more than at least 180 seconds in salt bath.
As the manufacture method of copper alloy hot forging described above, for example, can enumerate the 1st to the 3rd following manufacture method.
The 1st manufacture method is characterized in that, the Heating temperature of implementing before the forge hot of forging material of forge hot is 925～1025 ℃, and average crystallite particle diameter when the described heating of described forging material finishes is 0.10～5.0mm.
In addition, the forging material described in this specification sheets refers to and forges previous material and forge material afterwards.
The 2nd manufacture method is characterized in that, with 700 ℃ of above enforcements, be subjected at least 1 forge hot of the forging material of forge hot, after described forge hot, with 12 ℃/sec of above speed of cooling, described forging material is cooled to below 400 ℃, or the temperature province of 650 ℃ to 550 ℃, carry out cooling with 12 ℃/sec of above speed of cooling, carry out describedly described forging material being carried out to cold working after cooling, or do not carry out cold working and heat-treat, this heat treated condition is for as follows: the thermal treatment temp of 450～600 ℃ and hold-time are 0.2～10 hour, if described thermal treatment temp is made as to T ℃ and the described hold-time is made as to t hour, meet 520≤T+20 * t 1/2≤ 615 relation.Preferably after carrying out this thermal treatment, cooling until reach 400 ℃ with the speed of cooling of 0.1 ℃/min to 3 ℃/min.
In addition, with 700 ℃ of above enforcement forge hots, refer to the temperature before forging is made as more than 700 ℃.
About the copper alloy hot forging of manufacturing by the 2nd manufacture method, if preferably the electric conductivity after described forge hot and before described thermal treatment is made as to X (%IACS), between content [Mg] mass% of content [Sn] mass%, Mg of content [Fe] mass%, the Sn of content [Co] mass%, the Fe of content [P] mass%, the Co of X, P and content [Ni] mass% of Ni, have (45-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni])≤X≤(55-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]) relation.
The 3rd manufacture method is characterized in that, with 700 ℃ of above enforcements, be subjected at least 1 forge hot of the forging material of forge hot, after described forge hot, with more than 12 ℃/sec speed of cooling, the temperature province of 650 ℃ to 550 ℃, described forging material is carried out coolingly, describedly the temperature province of 400～540 ℃, keep 10～200 minutes after cooling.
In addition, with 700C, implementing above forge hot refers to the temperature before forging is made as more than 700 ℃.
According to the present invention, the intensity of copper alloy hot forging, endurance, heat conductivity and electrical conductivity are excellent.
Accompanying drawing explanation
Fig. 1 mean be external in crystal grain external circular diameter and in be connected to the figure of example of diameter of the inscribed circle of crystal grain.
Fig. 2 means the figure of the composition of the alloy of making hot forging.
Fig. 3 means the figure creating conditions of each operation of test 1.
Fig. 4 means the figure of the dull and stereotyped shape of forge hot in test 1.
Fig. 5 means the figure creating conditions of each operation of test 2.
Fig. 6 means the figure of the result of test 1.
Fig. 7 means the figure of the result of test 1.
Fig. 8 means the figure of the result of test 1.
Fig. 9 means the figure of the result of test 1.
Figure 10 means the figure of the result of test 1.
Figure 11 means the figure of the result of test 1.
Figure 12 means the figure of the result of test 1.
Figure 13 means the figure of the result of test 1.
Figure 14 means the figure of the result of test 2.
Figure 15 means the figure of the result of test 2.
Figure 16 means the photo of the metal structure in each test.
Embodiment
The copper alloy hot forging related to embodiments of the present invention describes.
As copper alloy of the present invention, the 1st invention alloy to the 3 invention alloys are proposed.In order to represent alloy composition, in this specification sheets, as the symbol of element of [Cu] band [] bracket, be expressed as the content value (mas s%) of this element.And, utilize the method for expressing of this content value, in this specification sheets, point out a plurality of calculation formula, but while not containing this element in each calculation formula as 0 calculating.And, the 1st to the 3rd invention alloy is generically and collectively referred to as to invention alloy.
The 1st its alloy composition of invention alloy be the Co, the P of 0.06～0.13mas s% that contain 0.21～0.44mass%, the Sn of 0.003～0.08mass% and 0.00003～0.0030mass% 0, remainder comprises Cu and inevitable impurity, has the relation of 3.1≤([Co]-0.005)/([P]-0.006)≤4.9 between content [Co] mass% of Co and content [P] mass% of P.
The 2nd its alloy composition of invention alloy be the compositing range of Co, P, Sn and 0 and the 1st invention alloy phase with, further contain the Zn of 0.001～0.3mass%, any more than a kind in the Ag of the Mg of 0.002～0.2mass%, 0.001～0.3mass%, remainder comprises Cu and inevitable impurity, has the relation of 3.1≤([Co]-0.005)/([P]-0.006)≤4.9 between content [Co] mass% of Co and content [P] mass% of P.
The 3rd its alloy composition of invention alloy is Co, P, Sn, 0, Zn, the compositing range of Mg and Ag and the 1st invention alloy or the 2nd invention alloy phase are same, the Ni that further contains 0.005～0.15mass%, any more than a kind in the Fe of 0.003～0.10mass%, remainder comprises Cu and inevitable impurity, content [Co] mass% at Co, the content of Ni [Ni] mass%, between content [P] mass% of the content of Fe [Fe] mass% and P, there is the relation of 3.1≤([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006)≤4.9 and 0.010≤2 * [Ni]+3 * [Fe]≤0.75 * [Co].
Then, manufacture method is described.Manufacture method has: heating process, carry out adding forge hot material before forge hot; Hot forging process, forges the forging material having heated; Refrigerating work procedure, the forging material after cooling forge hot; And separate out heat treatment step, heat cooling forging material afterwards.
Heating temperature in heating process is 925～1025 ℃.
Forge hot is at least carried out 1 time, and the temperature before forging to major general is made as more than 700 ℃.
In refrigerating work procedure, after forge hot, with 12 ℃/sec of above speed of cooling, be cooled to below 400 ℃, or the temperature province of 650 ℃ to 550 ℃, carry out cooling with 12 ℃/sec of above speed of cooling.
Separating out heat treated condition is, thermal treatment temp is that 450～600 ℃ and hold-time are 0.2～10 hour, if thermal treatment temp is made as to T ℃, hold-time, is made as t hour, meets 520≤T+20 * t 1/2≤ 615 relation.After this thermal treatment, preferably cooling until reach 400 ℃ with the speed of cooling of 0.1 ℃/min to 3 ℃/min.
Can and separate out at described refrigerating work procedure and between heat treatment step, carry out cold working.
Above manufacture method is called to the 1st manufacture method.
In addition, the manufacture resume of the forging material of the manufacture method of the copper alloy hot forging of confession present embodiment can be any.For example, after can be casting, extrude after, after forge hot and after cold working.
Can make the hot forging process in the 1st manufacture method afterwards as follows.With 12 ℃/sec of above speed of cooling, the temperature province of 650 ℃ to 550 ℃, carry out after forge hot coolingly, the temperature province of 400～540 ℃, keep 10～200 minutes afterwards.In this temperature province of 400～540 ℃, the effect of separating out heat treatment step in the 1st manufacture method is played in the maintenance of 10～200 minutes.
Above manufacture method is called to the 2nd manufacture method.
Then, the interpolation reason of each element is described.
While separately adding Co, cannot obtain higher intensity/electrical conductivity etc., but by the common interpolation with P and Sn, can not damage heat conductivity/electrical conductivity and obtain higher intensity, higher heat-resistant quality and higher ductility.While adding Co separately, for putting forward a little high-intensity degree, there is no unusual effect.If surpass the upper limit of the compositing range of invention alloy, not only effect is saturated, and does not damage heat conductivity/electrical conductivity on the contrary, and resistance to deformation during forging uprises.And Co is rare metal, so become expensive.If the content of Co is less than the lower limit of the compositing range of invention alloy, even if add altogether with P, also cannot obtain the higher endurance of object.Under the compositing range of Co, be limited to 0.21mass%, be preferably 0.24mass%, more preferably 0.27mass%, is 0.35mass% while especially needing higher endurance.While especially needing higher endurance, on the compositing range of Co, be limited to 0.44mass%, be preferably 0.43mass%, take into account endurance and cost aspect is preferably below 0.40mass%.
The interpolation of P, by adding altogether with Co and Sn, can not damage heat conductivity/electrical conductivity and obtain higher intensity.The independent interpolation of P improves mobility and intensity and makes crystal grain miniaturization.If the content of P surpasses the upper limit of compositing range, the effect of above-mentioned mobility, intensity, crystal grain miniaturization can be saturated.And heat conductivity/electrical conductivity is impaired.And, during casting, easily produce and break, during forge hot, also easily produce and break.If the content of P is less than the lower limit of compositing range, cannot bring into play high strength effect.In order to obtain higher endurance, the upper limit of the compositing range of P is 0.13mass% in the relation with Co, is preferably 0.12mass%.Under the compositing range of P, be limited to 0.060mass%, be preferably 0.070mass%, in order to obtain high endurance, it is 0.090mass%.
By add altogether Co and P in above-mentioned compositing range, intensity, energy of deformation after the creep properties at intensity, heat conductivity, electrical conductivity, ductility, 100～200 ℃, thermotolerance, brazing become good.If these two elements are solid solution condition, the resistance to deformation step-down while forging, and dynamic recrystallization and Static Recrystallization during forge hot are slow.When in the content of Co and P, a side is less than compositing range, not only above-mentioned any characteristic is not all brought into play significant effect, and heat conductivity variation very.When the content of Co and P is during more than compositing range, heat conductivity is similarly very poor, produce with interpolation separately each time identical shortcoming.These two elements of Co, P are for realizing the essential element of problem of the present invention, according to the cooperation ratio of suitable Co, P etc., do not damage heat conductivity/electrical conductivity and improve intensity and the high temperature creep strength after endurance, thermotolerance, hot strength, brazing.Co and P bring into play larger effect in the compositing range of invention alloy, and along with approaching the upper limit of compositing range, their various characteristics can further improve, but will take into account cost.Co, P bonding and make to contribute to the ultra tiny precipitate of intensity to be separated out.The common interpolation of Co and P suppresses the dynamic recrystallization in forge hot, postpones the generation of forge hot Static Recrystallization afterwards.But, about its effect, if surpass the upper limit of the compositing range of invention alloy, almost can't see the raising of characteristic, start on the contrary to produce shortcoming described above.
In order to obtain as the higher intensity of problem of the present invention and higher electrical conductivity, the ratio of Co and P is extremely important.If the conditions such as composition, Heating temperature, speed of cooling are complete, Co and P are probably approximately to arrive the approximately nano-precipitation of 3.5: 1 at 4: 1 by separating out the mass concentration ratio of thermal treatment formation Co:P.Precipitate is for example by Co 2p or Co 2. ap, Co xp ydeng chemical combination formula, represent, if roughly spherical or substantially elliptical and particle diameter are the size of 2～3nm left and right, contribute to very much intensity.Particularly, if the median size definition of the precipitate that the plane of usining in the cross section as forging shows, be that 1.5～3.9nm (is preferably 1.7～3.5nm, most preferably be 1.9～3.1nm), if or from the size distribution of precipitate, 90% of precipitate, more than 95% be preferably 0.7～7nm, more than 95% be most preferably 0.7～5nm, and precipitate separates out equably, can access high strength thus.
Precipitate distribute evenly and imperceptibly and size also consistent, its particle diameter is more tiny, more the particle diameter of recrystallize portion, intensity, hot strength is brought to impact.In addition, particle diameter about 0.7nm, using roughly the transmission electron microscope of ultra-high voltage (Transmission E1ectron Microscope, is below designated as TEM) with 750,000 times of observations, is to use special software can identify or the size of boundary that can size up.Therefore,, even if there is the precipitate less than 0.7nm, also, from except the calculating of above-mentioned median size, the scope of above-mentioned " 0.7～7nm " is equivalent in meaning with " 7nm is following ".In addition, precipitate is not certainly included in the crystalline substance that cast sections produces and goes out thing.And, if dare to define the dispersed of precipitate, during with the tem observation of 750,000 times, in the region of 200nm * 200nm arbitrarily of microscopic examination described later position (except special parts such as utmost point top layers), more than at least 90% precipitate particle in abutting connection with precipitate particle spacing, be below 100nm, be preferably below 75nm, or in 25 times of median size, or in the region of 200nm * 200nm arbitrarily of microscopic examination described later position, precipitate particle exists more than at least 25, be preferably more than 50, at the fine position of standard, characteristic is not brought to the larger without separating out band of impact, can be defined as and there is no the inhomogeneous band of separating out.
About the size of precipitate, if the median size of precipitate surpasses 3.9nm, the contribution of intensity is diminished, if median size is less than 1.3nm or 1.5nm, also can be saturated in intensity, heat conductivity/electrical conductivity is poor.If the size of precipitate is less than 1.5nm, heat conductivity/electrical conductivity is poor, if this is because too fine, is difficult to separate out all.In addition, the median size of precipitate is preferably below 3.5nm, when especially the metal structure after forge hot consists of recrystal grain, due to because of precipitate reinforced alloys, so the median size of precipitate is preferably below 3.5nm, most preferably is below 3.1nm.From the relation with heat conductivity/electrical conductivity, consider, more than lower limit side is preferably 1.7nm.And, even if median size is less, if the shared large percentage of thick precipitate can not work to intensity.That is, the larger precipitate particle that surpasses 7nm not too contributes to intensity, so separate out particle diameter, is that ratio below 7nm need to, for more than 90%, be preferably more than 95%.And if the inhomogeneous dispersion of precipitate is without separating out band, intensity is lower.About precipitate, most preferably meet median size less, there is no thick precipitate, separate out this 3 conditions equably.In addition, when the addressed value of separating out heat-treat condition formula described later is during lower than lower value, although precipitate is fine, the amount of separating out is less, therefore also variation of and heat conductivity less to the contribution of intensity.When the value of separating out heat-treat condition is during higher than higher limit, heat conductivity can improve, but precipitate becomes large, and the big particle that surpasses 7nm increases, and the quantity of precipitate particle reduces, and the contribution to intensity based on separating out diminishes.
In the present invention, even if the amount of Co and P is desirable cooperation, and even separate out thermal treatment with desirable condition, all Co and P can not form precipitate yet.In the present invention, if can and separating out heat-treat condition and separate out thermal treatment in the Co of industrial enforcement and the cooperation of P, the roughly 0.005mass% of Co and the roughly 0.006mass% of P be not suitable for forming precipitate, with solid solution condition, are present in matrix.Therefore, need to deduct respectively from the mass concentration of Co and P the mass ratio that 0.005mass% and 0.006mass% decide Co and P.; determine the composition of Co and P or only determine that the ratio of Co and P is inadequate, the value of ([Co]-0.005)/([P]-0.006) is 3.1～4.9 conditions that are absolutely necessary, and is preferably 3.2～4.6; more preferably 3.3～4.3, most preferably be 3.5～4.0.If best ratio is ([Co]-0.005) and ([P]-0.006), can forms the nano-precipitation of object, and can access higher heat conductivity/electrical conductivity and high strength.On the other hand, if depart from above-mentioned ratio ranges, a wherein side of Co and P is not suitable for forming precipitate and is solid solution condition, not only can not get high strength, and also variation of heat conductivity/electrical conductivity.Or, form the precipitate different from targeted composition and division in a proportion rate, separate out particle diameter and become large or into not too contributing to the precipitate of intensity, so can not become the material of heat conductivity/electrical conductivity, intensity, creep properties excellence.
Then, Sn is described.A small amount of content that Sn is usingd more than 0.003mass% was hankered as adding of the initial operation of forge hot, heating by the short period of time at more than 925 ℃ temperature promotes the solid solution of Co and P and makes coarse grains, dynamic recrystallization while on the other hand, suppressing forge hot and the generation of Static Recrystallization.And even if material temperature during forge hot locally declines, need the time when the local difference of degree of finish and forge hot, the interpolation of Sn also has the effect of the solid solution condition that keeps Co and P.The interpolation of Sn has following effect: in the initial heating phase as thermal forging technology, make metal structure thick, and make Co and P more promptly be solid solution condition; In the forge hot process segment, the solution susceptibility such as Co, P are declined, keep solution state; While finally separating out, separate out in a large number and take the precipitate that Co and P be main body, and these precipitates are fine and disperse equably and separate out.Metal structure aspect, performance is effect as follows: during the more than 925 ℃ high temperature of the heating before forging, the coarsening of promotion crystal grain; In forge hot, suppress to generate recrystallization nucleus.By the common interpolation of Co, P and Sn, under the forging temperature of regulation, make in this application Co, P etc. be that solid solution condition refers to the resistance to deformation that reduces under forge hot and with less power moulding.On the other hand, the dynamic recrystallization while suppressing forge hot and the generation of Static Recrystallization core also postpone dynamic recrystallization and Static Recrystallization refers to, the recrystallization temperature while improving forge hot, easily obtains non-recrystallization state in the metal structure after forging.Although also depend on the working modulus of forge hot, if by forge material be temporarily heated to be 925 ℃ above and also forge before temperature at Co and P, between 700 ℃ to 850 ℃ in solid solution condition, can obtain the target worked structure in the application.And heat conductivity and electrical conductivity be proportional relation roughly generally, but thermal forging technology separates out to the effect of the Sn of the effect of perfect condition Co, P etc. to combine and heat conductivity improves to more than proportionlity with having.And, by the solid solution of Sn, improve the thermotolerance of the matrix of hot forging, thereby have still, compared with highland, keep brazing endurance afterwards and the effect that improves creep properties.
In order to bring into play the effect of Sn described above, the content of Sn need to be for more than 0.003mass%, but for further its effect of performance, more than being preferably 0.005mass%, more than most preferably being 0.007mass%.On the other hand, if the content of Sn surpasses 0.08mass%, its effect can be saturated, electricity/heat conductivity variation.When further needing heat conductivity and electrical conductivity, be preferably below 0.06mass%, although have and intensity and stable on heating relation, be preferably below 0.04mass%.
Then, Zn, Mg and Ag are described.Zn, Mg and Ag put forward heavy alloyed intensity by solution strengthening, have with Sn simultaneously and in a succession of technique of forge hot, keep in the same manner the solid solution condition of Co and P and postpone the effect of dynamically/Static Recrystallization.Zn further improves welding wettability and solderability.Zn etc. have the effect that promotes that Co and P evenly separate out.And Ag and Mg improve endurance and the creep properties after brazing.If the content of Zn, Mg and Ag is less than the lower limit of compositing range, do not bring into play above-mentioned effect.If surpass the upper limit of each compositing range, not only above-mentioned effect can be saturated, and heat conductivity starts to decline, and it is large that resistance to deformation during forge hot becomes, energy of deformation variation.The upper limit of the compositing range of Zn is preferably below 0.2ma ss%, more preferably below 0.1mass%.Equally, more than the content of Mg is preferably 0.003mass%, 0.005mass% above.The upper limit of the compositing range of Mg is preferably below 0.1mass%, more preferably below 0.05mass%.More than the content of Ag is preferably 0.003mass%, 0.005mass% above.On the other hand, the upper limit of the compositing range of Ag is preferably below 0.2mass%, more preferably below 0.1mass%.
Then, Fe and Ni are described.Fe and Ni replace a part for Co function, and performance simultaneously makes the effect that the bonding of Co and P further carries out effectively.Therefore,, if add Ni and Fe, according to the relational expression of the Co with basic and P, further set up following two relational expressions.
3.1≤([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006)≤4.9 (preferable range is 3.2～4.6, more preferably 3.3～4.3, most preferably be 3.4～4.0),
0.010≤2 * [Ni]+3 * [Fe]≤0.75 * [Co] (preferable range is 0.025～0.7 * [Co], and more preferably 0.040～0.6 * [Co], most preferably is 0.050～0.5 * [Co]),
0.8 the coefficient of 0.9 the coefficient of [Ni] and [Fe] represents the ratio of the bonding of Co and P to be made as the ratio of 1 o'clock Ni and Fe and P bonding.In addition, if the scope of the proportioning renunciation formula of Co, Fe, Ni, P etc., precipitate reduces, and the miniaturization of damage precipitate and dispersed, the undue solid solution such as C o, Fe, Ni or P that does not participate in separating out is in matrix, heat conductivity/electrical conductivity variation, the while cannot obtain the higher endurance of target.In the present invention, if coordinating and separate out heat-treat condition and separate out thermal treatment with P's at Co, Ni, the Fe of industrial enforcement, in ([Co]+0.9 * [Ni]+0.8 * [Fe]), the roughly 0.005mass% of Co and the roughly 0.006mass% of P are not suitable for forming precipitate, with solid solution condition, are present in matrix.Therefore, need to deduct respectively from the mass concentration of ([Co]+0.9 * [Ni]+0.8 * [Fe]) and P the mass ratio that 0.005mass% and 0.006mass% decide Co etc. and P.And the mass concentration ratio that the precipitate of its Co etc. and P need to form Co:P is roughly a part 4.3: 1 to 3.5: 1, for example Co with Co 2p, Co 2.ap or Co 1.bcentered by P, be substituted by the Co of Ni and Fe xni yfe zp a, C o xni yp z, Co xfe yp zdeng.If do not form with Co 2p or Co 2.xp yfor basic nano-precipitation, cannot obtain the higher endurance as the theme of this case, higher heat conductivity/electrical conductivity and brazing higher endurance or creep properties afterwards.
The independent interpolation of Fe and Ni reduces heat conductivity/electrical conductivity, and resistance to deformation during forge hot uprises.And Ni is under the prerequisite of the common interpolation with Co and P, except having the replacement function of Co, the reducing amount of the heat conductivity/electrical conductivity based on Ni is less.
Even if the value of mathematical expression ([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006) departs from 3.1～4.9 central value, Fe and Ni also have the reduction of electroconductibility are limited in to minimal function.But, if add the above Ni of 0.15mass% or the excessive interpolation of mode over 0.8 * [Co] with the value of mathematical expression (2 * [Ni]+3 * [Fe]), the composition of precipitate slowly changes, not only inoperative to intensity raising or stable on heating raising, and thermal distortion resistance during forge hot increases, heat conductivity/electrical conductivity reduces.
Fe, under the prerequisite of the common interpolation of Co and P, improves intensity with indium addition, and postpones dynamic recrystallization and increase non-recrystallization tissue.But, if the content of Fe surpasses 0.10mass% or surpasses the excessive interpolation of the mode Fe of [Co] with the value of mathematical expression (2 * [Ni]+3 * [Fe]), the composition of precipitate slowly changes, not only do not improve intensity or thermotolerance, and the increase of thermal distortion resistance, heat conductivity/electrical conductivity reduces.
Then, metal structure is described.
Hot forging generally has complicated shape, according to each position, with various working moduluses, carries out hot-work.And, also depend on by various conditions such as the heating condition of forging material of forge hot or the number of times of forge hot, hot forging temperature, but the metal structure obtaining in forge hot is different according to each position of hot forging.In order to obtain the hot forging of the high endurance of having of the application, high thermal conductivity and high electrical conductivity, needing average crystallite particle diameter is adding up to more than 80% of the shared ratio of the shared ratio of the recrystal grain group of 0.050mm～0.50mm and non-recrystallization crystal grain.Alloy of the present invention has the character of the generation that suppresses recrystallization nucleus in forge hot, but when in hot forging temperature, higher and hot-work rate is lower, the metal structure of hot forging carries out recrystallize.But, if the average crystallite particle diameter of recrystal grain is the recrystal grain group below 0.050mm, shared ratio is more than 20%, it is large that the median size of the Co generating when the next one is separated out thermal treatment and the precipitate of P becomes, and separates out insufficiently a little, cannot obtain high endurance on the whole.And electric and hot conductivity is variation also.If the average crystallite particle diameter of recrystal grain is more than 0.050mm, the median size of the Co generating when separating out thermal treatment and the precipitate of P diminishes, and can obtain high endurance on the whole.And, if average crystallite particle diameter is more than 0.050mm,, except the separating out of strengthening and Co and P, also postpone the diffusion of the Constitution Elements such as Co, P, Sn, so can improve the thermotolerance of matrix, and can improve endurance and creep properties at 100～200 ℃ as the application's environment for use.And, if average crystallite particle diameter is more than 0.050mm,, when the brazing of approximately 800 ℃, can make the solid solution again of Co and P slow, and the nano-precipitation of residual Co and P, so also can obtain higher endurance after brazing.And, while further implementing cold working after forge hot, due to remaining its processing strain, so can obtain higher endurance.In addition, the recrystal grain group that is 0.050mm～0.50mm as average crystallite particle diameter, more than their average crystallite particle diameter is preferably 0.070mm, more than most preferably being 0.080mm.On the other hand, if average crystallite particle diameter surpasses 0.50mm, between producing aspect ductility, inscribe.More preferably, below 0.30mm, most preferably be below 0.20mm.
If the state that the metal structure of hot forging is non-recrystallization, can be before forge hot heating time the average crystallite particle diameter that produces be to accumulate strain in crystal grain more than 0.1mm, so can with separate out thermal treatment after the existence of fine precipitate particle combine and obtain higher endurance.And, can improve endurance and creep properties at 100～200 ℃ as environment for use.Due to the precipitate of separating out precipitate particle in non-recrystallization crystal grain and becoming the recrystal grain group of being a bit larger tham the average crystallite particle diameter having more than 0.050mm, so the contribution to endurance based on precipitate diminishes, but the strain during due to forge hot increases, so the contribution to endurance based on strain becomes greatly.When temperature when the working modulus of forge hot is higher or before forging is lower, the endurance with the invention alloy of non-recrystallization crystal grain slightly uprises, but average crystallite particle diameter is that more than 0.050mm recrystal grain group and non-recrystallization intergranule are without the larger difference of endurance, heat conductivity and electrical conductivity on the whole, if therefore exist their shared ratios to add up to more than 80%, become the hot forging with high endurance, high thermal conductivity and high electrical conductivity.Certainly, can there is higher endurance and creep properties as at 100～200 ℃ of environment for use.In addition, the non-recrystallization tissue generating in forge hot is similar to the worked structure shape producing in cold forging or cold working, but that its dislocation desity is compared in the worked structure forming with cold working is lower, is therefore rich in ductility.
If following condition when any is complete, the shared ratio of recrystal grain group that the average crystallite particle diameter of hot forging is 0.050mm to 0.50mm becomes more than 60%, and can obtain having the hot forging of high endurance, high thermal conductivity and high electrical conductivity.
1., even in hot forging, working modulus is when also integral body is lower
2. the crystal grain of the forging material before forge hot is during coarsening
3. because hot forging is when greatly easily causing Static Recrystallization and easily carrying out crystalline growth
4. when hot forging temperature is higher
Further optimum condition as the average crystallite particle diameter of hot forging, average crystallite particle diameter is that the shared ratio of the recrystal grain group of 0.080mm to 0.30mm is more than 60%, or the shared ratio of the recrystal grain group that average crystallite particle diameter is 0.050mm to 0.50mm is more than 80%, the shared ratio of recrystal grain group that most preferably average crystallite particle diameter is 0.080mm to 0.20mm is more than 80%.By being made as the state of these metal structures, be made as the average crystallite particle diameter that is greater than general copper alloy, the median size of the Co generating while separating out thermal treatment and the precipitate of P diminishes and can obtain high endurance, even if carry out brazing, also hinder the solid solution again of precipitate particle, if forging is further implemented to cold working, can in crystal grain, accumulate more its processing strains, therefore can there is higher endurance.If crystal grain is larger, there is the effect of the diffusion that postpones atom, therefore can improve endurance and creep properties at 100～200 ℃ as environment for use.In addition, if average crystallite particle diameter surpasses 0.50mm, aspect ductility, have problems.Average crystallite particle diameter more preferably, below 0.30mm, most preferably is below 0.20mm.
In addition, after forge hot and separate out average crystallite particle diameter is 0.050mm to 0.50mm before thermal treatment the shared ratio of recrystal grain group be more than 60% hot forging after forge hot and separate out the moment before thermal treatment, endurance is 60～130N/mm 2, Vickers' hardness is 50～85, and electric conductivity is 33～49%IACS.Owing to separating out, thermal treatment intensity is before lower, so easily correct or be easily shaped to target shape.And, sometimes according to the shape of hot forging, after forge hot and before separating out thermal treatment, implement 1～20% lighter cold working.By implement lighter cold working after forge hot, the endurance of the hot forging after thermal treatment significantly improves.Particularly, by 5～15% to be cold worked into be 280～390N/mm 2endurance, and become the hot forging that further preferred radiator element or short-circuited conducting sleeve are used.In addition, can improve endurance and the creep properties at 100～200 ℃ as environment for use.Particularly, as the 100N/mm that loads at 200 ℃ 2stress, and while carrying out the creep test of 1000 hours, become and do not comprise that the total creep deflection of initial deformation is the hot forging of the resistance to creep strain excellence below 0.15%.
Even if the crystallization particle diameter of the forging material before forging is larger, when for following situation, the metal structure of hot forging also becomes non-recrystallization state.
1. when forge hot working modulus is larger
2. in being forged into the position etc. of thin-walled, while comprising forge hot when interior temperature declines sharply and not have to produce the time of dynamic/Static Recrystallization
3. when hot forging temperature is lower
Even hot forging temperature is lower and the metal structure of hot forging in non-recrystallization state, forging material is also at least temporarily heated to be more than 925 ℃, so the precipitate of separating out after thermal treatment is fine, alloy is reinforced, after thermal treatment, be also equivalent to the strain of having accumulated of non-recrystallization state during residual forge hot simultaneously, and it is added in together, therefore can obtain high endurance, high thermal conductivity and high electrical conductivity.In addition, because original crystal grain is non-recrystallization state, so even if carry out brazing, the disappearance of precipitate is also slow, and can improve endurance and the creep properties at 100～200 ℃ as environment for use.If the shared ratio of non-recrystallization crystal grain is more than 60%, can obtain having the hot forging of high endurance, high thermal conductivity and high electrical conductivity.As further optimum condition, the shared ratio of non-recrystallization crystal grain is more than 80%.
Then, manufacturing process is described.
Heating temperature before forging need to be heated to be 925 ℃ above (being preferably more than 940 ℃) by forging material.If be heated to be more than 925 ℃, also have the effect containing Sn, Co and P solid solution are in matrix, and the crystal grain-growth restraining effect of the precipitate based on Co and P disappears, so become average crystallite particle diameter, is thick metal structure more than 0.10mm.If be temporarily heated to be the more than 925 ℃ of metal structure coarsening by forging material, even if the temperature at hot forging when adding that the process furnace temperature of forge hot material reduces and reduce and carry out repeatedly forge hot from stove to the temperature of forging material before forging reduces, also can maintain the solid solution condition of Co and P.For example, when making annular large-scale short-circuited conducting sleeve, will forge material and forge more than 10 times, and from forge hot, start to need 5 minutes to 15 minutes till finishing, if but finally hot forging temperature is for more than at least 700 ℃, and most of Co and P are in solution state.
And, because the crystal grain of coarsening postpones the generation of the recrystallization nucleus in forge hot, so more than the average crystallite particle diameter of its generation is made as to 0.050mm, further be made as large-size more than 0.080mm, or the average crystallite particle diameter that makes generation when forge hot is heated is the state that crystal grain more than 0.1mm is distortion, even if it is non-recrystallization state.And, if the crystal grain of hot forging is larger, when the brazing of approximately 800 ℃, postpone by separating out Co that thermal treatment separates out and the solid solution again of P.
If Heating temperature lower than 925 ℃ and average crystallite particle diameter less than 0.10mm, along with temperature in forge hot reduces and the process of forge hot time and cannot maintain the solid solution condition of Co, P etc., start to separate out the thick precipitate that intensity is not too worked, even separate out thermal treatment after forging, the surplus energy of separating out also diminishes, and therefore cannot obtain higher endurance.And, at this, separate out the particle of separating out in thermal treatment and also become and be greater than situation about making more than the temporary transient thick 0.1mm of turning to of average crystallite particle diameter, thus higher endurance cannot be obtained, and also cannot obtain higher creep properties.And electricity/heat conductivity is also poor.
If forging material is temporarily heated to be more than 925 ℃, and forge at the temperature below 850 ℃, in thinner wall section, speed of cooling is very fast, forges the crystal grain of material by heating coarsening, Co, P etc. are in solid solution condition and contain Sn, and metal structure is non-recrystallization state thus.For example, heating during cooling forging material in continuous oven, will be up to Da Wendu and be made as more than 925 ℃, then be reduced to the preset temperature between 700 ℃ to 850 ℃, in stove, on purpose control temperature and carry out forge hot, can stably obtain target non-recrystallization tissue thus.By the strain of accumulating based on non-recrystallization state with separate out two the effect reinforced alloys of separating out of nano-precipitation after thermal treatment.In addition, if 925 ℃ of average cooling rates to described preset temperatures are more than 3 ℃/min, be preferably more than 5 ℃/min, almost maintain Co in alloy and the solid solution condition of P.And, the temperature coarsening due to the crystal grain of forging material during since the forge hot of 800 ℃ of left and right, Co, P etc. are in solid solution condition, and contain Sn, even thus at the lower heavy section of hot-work rate, also some is non-recrystallization state to metal structure.But, even because the Co in alloy or P how much in solid solution condition, hot forging temperature also reduces, and forge hot resistance to deformation uprises, so in view of the power of swaging machine and determine forging temperature with the relation of formability.About alloy of the present invention, even if forging temperature step-down, with in the same manner described, even arrive to the elapsed time till predetermined lower temperature from being up to Da Wendu, because Co and P are in solid solution condition, so its thermal distortion resistance is also excellent far below other precipitation type copper alloys and energy of deformation.
The temporary transient short period of time is heated to be more than 925 ℃, and makes to forge the crystal grain-growth of previous forging material, and average crystallite particle diameter is made as to 0.10mm to 5.0mm.Can by grain size number is made as 0.10mm with on make most of Co, P etc. become solid solution condition.
And, if at high temperature make raw-material coarse grains, even if on purpose reduce forging temperature (temperature before forging is more than 700 ℃), and repeatedly carry out forge hot and temperature reduction or spended time, also Co, P etc. can be remained to solid solution condition.If the crystal grain of coarsening is carried out to forge hot with 850 ℃ of following temperature, can make metal structure become non-recrystallization state, if non-recrystallization state can make strain accumulate in hot forging.When separating out thermal treatment, the precipitate of Co, P is separated out imperceptibly, and the strain of accumulating during forge hot is further added together, and the endurance that therefore can make to separate out after thermal treatment further uprises.And, can improve endurance and creep properties at 100～200 ℃ as environment for use.The forging temperature that is used for being made as non-recrystallization crystal grain is more preferably below 830 ℃, lower in limited time because resistance to deformation uprises, so to be preferably more than 720 ℃, more preferably 750 ℃ are forged above, temperature province till 400 ℃ is cooling with the speed of cooling of 12 ℃/sec, separate out afterwards thermal treatment, if can become like this hot forging of the higher and heat conductivity/electrical conductivity excellence of endurance.
Can with after forge hot and the electric conductivity of separating out the forging before thermal treatment differentiate Co, P etc. and whether in solid solution condition and forging, whether separate out surplus energy.About the strengthening of the alloy based on separating out, except the size of the particle diameter of precipitate, whether have and separate out surplus energy for another larger main points.If meet the application's alloy composition, the electric conductivity after forge hot and before thermal treatment: the value of %IACS serve as reasons (45-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]) the value that represents of formula more than, be preferably by (55-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]) the value that represents of formula below.Lower limit is the desired quantity in solid solution condition such as Co, P in industrial forge hot, and upper limit side is to realize the numerical value that remains the boundary of separating out surplus energy in the application's aspect forging.Upper limit side be preferably (52-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]).Although also depend on the content of Co, P etc., because the electric conductivity after forging is 33～49%IACS, the electric conductivity after thermal treatment is more than 75%IACS, so it is poor larger, more demonstrates the larger amount of separating out.From the viewpoint of the amount of separating out, the difference of separating out the electric conductivity of thermal treatment front and back is required to be 32%I ACS, more than being preferably 36%IACS, more than most preferably being 40%IACS.
When not reaching for example heating of 900 ℃ of preset temperature, due to most of end of solid solution of Co, P etc., so if forge hot at once after heating, and water-cooled at once, and separate out thermal treatment, can arrive to the endurance that approaches target.Yet, during time after heating till spending forge hot, or the temperature of implementing repeatedly forge hot and forging is reduced to while approaching 750 ℃, or while needing the time till cooling after forge hot, if Heating temperature is lower than 925 ℃, Co and P cannot keep solid solution condition and separate out larger precipitate particle.Even if implement to separate out thermal treatment, the precipitate particle of separating out is also greater than and forgings material is heated to be before forge hot to 925 ℃ above time.Its result, becomes and on average separates out the precipitate particle that particle diameter is larger, surpasses the precipitate of 4nm or 0.7～7nm size less than 90%, does not reach required endurance.On metal structure, if the heating of forging material lower than 925 ℃, crystal grain can not become greatly, about forge hot metal structure afterwards, even if be recrystal grain, average crystallite particle diameter is that the ratio below 0.05mm is also more.And even if be non-recrystallization crystal grain, the crystal grain of original forging material is also less.According to these, it is large that the particle diameter of precipitate particle becomes, endurance step-down, and also variation of the creep properties at 100～200 ℃, even after soldering, endurance is also lower, and creep properties is variation also.
After heat, without horse back forge hot, and can repeatedly forge.Yet, in order to keep the solid solution condition of Co and P, by forging temperature be at least made as 700 ℃ with on implement final forging, cooling in view of formability or in forging, need to preferably be made as more than 730 ℃.
Then, to cooling the describing after forge hot.
After carrying out forge hot with 700 ℃ of above temperature, below 400 ℃ with more than 12 ℃/sec, be preferably 20 ℃/sec of above speed of cooling quenchings, or after forge hot, with more than 12 ℃/sec, be preferably 20 ℃/sec of above speed of cooling by the temperature province of 650 ℃ to 550 ℃, this becomes absolute condition when cooling.
Preferred water-cooled generally, but need rapidly by separating out the region of 650 ℃ to 550 ℃ of the temperature of beginning.If slowly by this temperature province, separate out the thick precipitate that intensity is not too worked, even after separate out thermal treatment in heat-treat, the particle of separating out is also larger, on average separate out particle diameter and surpass 4nm, or the precipitate of 0.7～7nm size is less than 90%, so endurance does not reach required numerical value.
Then, to separating out thermal treatment, describe.
After cooling after forge hot, in order to make Co and the P of solid solution separate out and separate out thermal treatment.Intensity after thermal treatment depends on separates out particle diameter.Hour, the intensity of copper alloy hot forging uprises the particle diameter of precipitate particle.
Separating out heat treated condition is made as follows: if thermal treatment temp is made as to T ℃ and will the hold-time be made as t hour, meet 520≤T+20 * t 1/2≤ 615 relation.Wherein, in described relational expression, T ℃ is 450～600 ℃, within t hour, is 0.2～10 hour.
Separating out heat treated further preferable range is 530≤T+20 * t / 2≤ 590, T ℃ is 470～570 ℃, within t hour, is 0.3～8 hour.If the temperature province in predetermined temperature to 400 after separating out thermal treatment ℃ is cooling with the speed of cooling below 3 ℃/min, electricity/heat conductivity can improve.For example, compare when cooling with 50 ℃/min, when cooling with 1 ℃/min, electric conductivity improves about 2%IACS.In addition, to show greatly the speed of cooling of 0.3 ℃/min saturated for its effect.And, in the relation of electricity/heat conductivity and tensile strength and endurance, when paying attention to intensity, be preferably 525≤T+20 * t 1/2≤ 570, when paying attention to electricity/heat conductivity, be preferably 560≤T+20 * t 1/2≤ 605.According to necessary characteristic, can suitably set heat-treat condition.
Separate out heat treated basic be reheating after cooling described above, but in the process of cooling after forge hot, after the temperature province of 650 ℃ to 550 ℃, can be in the region of 540～400 ℃ cooling or keep in its temperature province with the speed of cooling below 2 ℃/min.The precipitate of Co and P is separated out imperceptibly.At this moment, just there were sufficient effect the cooling time in the region of 540～400 ℃ or hold-time with 10 minutes to 200 minutes, can take into account separate out cooling.About forging material, when carrying out forge hot, the state of metal structure is according to position or be recrystal grain or be non-recrystallization crystal grain, or at average crystallite particle diameter or to process the aspect such as residual of strain variant, becomes inhomogeneous state.Yet, by this thermal treatment, combine and eliminate residual stress with separating out processing, so metal structure can be made as to uniform state.
Can be after forge hot cooling and separate out and carry out cold working between thermal treatment.After forge hot, if carry out gagging and cold working, for example, further carry out cold forging, do not damage heat conductivity/electrical conductivity and improve endurance or creep properties.And, in heavy section, the average crystallite particle diameter of hot forging is more than 0.05mm, more than being preferably 0.08mm, or the thick 0.1m m that turns to of original average crystallite particle diameter of non-recrystallization portion, so even the condition of brazing is the high temperature of 800 ℃, if the short period of time, also can postpone the solid solution again of Co and P.And, when imposing cold working, owing to postponing the recovery of processing strain, so endurance or creep properties after brazing uprise.
In addition, if hot forging is carried out to air cooling after the brazing of 800～850 ℃, heat conductivity/electrical conductivity variation.This be because, even if be the high temperature of 800 ℃, if the short period of time, the solid solution again of Co and P is also slow, but Co and P can solid solutions, that need to carry out Co and P separates out processing again.In process of cooling after brazing, with the temperature of 500～650 ℃, keep 5～100 minutes, if consider productivity, can keep 5～50 minutes with the temperature of 550～650 ℃, or the temperature province of 550～650 ℃ cooling 5～50 minutes.Or after brazing, temporary transient air cooling, keeps 5～100 minutes with the temperature of 500～650 ℃, if consider productivity, keeps 5～50 minutes with the temperature of 550～650 ℃, so just can again have like a cork higher heat conductivity/electrical conductivity.Thermal treatment after this brazing mainly take that to improve heat conductivity/electrical conductivity be object, from improve the forge hot of endurance and heat conductivity/electrical conductivity after to separate out thermal treatment different and make a distinction.
(embodiment)
Use above-mentioned the 1st invention alloy, the 2nd invention alloy, the 3rd invention alloy and relatively use the copper alloy made high-performance hot forging forming.Fig. 2 represents to make the composition of the alloy of hot forging.And, also use fine copper C1220 and C1020 to use as a comparison.
As test 1 following manufactured copper alloy hot forging.
First, by electric furnace dissolving starting material the adjustment composition of true-time operation, producing external diameter is the steel billet that 240m m, length are 700mm.At 870 ℃, by heating steel billet 2 minutes, by indirect extrusion press, extrude the rod that external diameter is 36.5mm.The plasticating capacity of indirect extrusion press is 2750 tons.The average crystallite particle diameter of hot extrusion material is 0.030mm to 0.045mm.
Using hot extrusion material as forging material, Heating temperature, forging temperature before forging by change, forge end temp, forge the speed of cooling after finishing, a plurality of operation manufactured copper alloy hot forgings of separating out heat-treat condition.Creating conditions of each operation shown in Fig. 3.
Operation A, A-1, A-2, C, E, F, G, H, H-1 are the operation that is suitable for above-mentioned the 1st manufacture method.
Step D, I, J are the operation of the comparative example of the 1st manufacture method.
Process B is the operation that is suitable for above-mentioned the 2nd manufacture method, after forge hot, impregnated in the salt bath of 500 ℃ and keeps 30 minutes.
Operation S is the operation that is suitable for fine copper C1220 and C1020.
About forging shape, the hot extrusion material of horizontal φ 36.5mm, L=152mm, the flat board of the heavy section that forge hot becomes to comprise 20mm and the thinner wall section of 6mm, forges respectively a plurality ofly, and separates out thermal treatment.The dull and stereotyped shape of forge hot shown in Fig. 4.The dull and stereotyped corresponding hot extrusion material of long side direction extrude direction.After heating before forge hot, carry out water-cooled and observe the metal structure in cross section.
In forging wherein 1 directly by Amsler vibraphone universal testing machine, carry out tension test, obtain endurance.
About another forging, heavy section is made as X portion (2 positions), and thinner wall section is made as Y portion, and the boundary portion of heavy wall and thin-walled is made as Z portion and cuts out, by Amsler vibraphone universal testing machine, X, Y portion are carried out to tension test, measure endurance, extensibility, tensile strength.
About other 2 forging, cut off any part, metal structure is observed respectively in 10 places separately by the X of 1 forging, Y, Z portion therein, obtains the average crystallite particle diameter that has or not recrystallize and recrystal grain.Measure thermal conductivity and the conductivity of X, Y portion simultaneously.The thermal conductivity of forging and conductivity adopt the mean value of X, Y portion.
From forging, cut out 1 X portion, at 200 ℃, apply 50N/mm 2stress, and carry out the creep test of 1000 hours, measure the total creep deflection that does not comprise initial deformation.
And, from forging, cut out 2 X portions, be equivalent to the test of soldering, in the salt bath of 825 ℃ that is equivalent to actual Ag soldering condition, heated for 300 seconds, the thermal treatment of again implementing 30 minutes dippings after air cooling in the salt bath of the 590 ℃ line space cold (following, this test is called to soldering and quite tests) of going forward side by side.In addition, this test portion be impregnated in the salt bath of 825 ℃, its result reached 800 ℃ after dipping between 85 seconds to 105 seconds.Therefore, mean at 800 ℃～825 ℃ and more than at least 180 seconds be heated to high temperature.The suitable test film of processing soldering applies 50N/mm at 200 ℃ 2stress, and carry out the creep test of 1000 hours, except initial deformation, measure total creep deflection.
As test 2, by diameter, be that the slab that 240mm, length are 80mm is heated to 950 ℃, repeatedly carry out forge hot, obtain external diameter and be about 300mm, internal diameter and be about 90mm, be highly the forge hot sheet of about 50mm.After forging, to forge 650 ℃ of end temps, carry out air cooling.
Using this forge hot sheet as forging material, a plurality of operations of creating conditions by change are manufactured hot forging.In gas furnace, to forging material, reheat, by forge hot, making external diameter is that about 350mm, internal diameter are about 200mm, are highly the ring of about 50mm.Forging times is approximately 20 times.A part is further carried out cold forging, is highly made as 44mm.This processing is equivalent to 12% cold working rate.Heating temperature, forging temperature, forging end temp, the forging having changed before forging of creating conditions finishes speed of cooling afterwards, separates out heat-treat condition.Creating conditions of each operation shown in Fig. 5.
Operation K, K-1, L, M are the operation that is suitable for above-mentioned the 1st manufacture method.
Operation N, 0, P, Q, R are the operation of the comparative example of the 1st manufacture method.
Operation T is the operation that is suitable for fine copper C1220 and C1020.
Separate out after thermal treatment, cutting out with the cross section of testing the X portion same size of 1 forging test sheet is the test film that 20mm * 20mm, length are 160mm, carries out metal structure observation, the mensuration of thermal conductivity/conductivity, the soldering in cross section and quite tests and creep test.With regard to creep test, when there is no cold forging, at 200 ℃, apply 50N/mm 2stress, and in having carried out the test of cold forging, at 200 ℃, apply 100N/mm 2stress, and carry out the creep test of 1000 hours, except initial deformation, measure total creep deflection.No matter the suitable test of soldering has or not cold forging, all in the salt bath of 825 ℃, heats for 300 seconds.After air cooling, again in the salt bath of 590 ℃, flood 30 minutes, implement to be mainly used in the thermal treatment of separating out of recovery heat/conductivity, carry out afterwards air cooling.In addition, about using the test of C1020, C1220, do not implement this and separate out thermal treatment.Measure endurance, thermal conductivity, the conductivity of the suitable test film of this soldering.In addition, the suitable test film of processing soldering applies 50N/mm at 200 ℃ 2stress, and carry out the creep test of 1000 hours, except initial deformation, measure total creep deflection.
In following test, test 1 and test each hot forging of 2 comment value.
Carry out as follows tension test.
Ring forging about heavy section (X portion) and test 2, cuts out test film, and tests according to No. 4 test films of the metal material stretching test sheet as JIS Z2201.Wherein, the diameter of parallel portion is made as to 10mm, and gauge length is made as to 4 * A 1/2(sectional area that A is parallel portion).For test 2 ring forging, by width for central authorities and to comprise cross section surface, that have 20mm * 20mm, cut out into length be that the rectangular parallelepiped of 160mm is made as test film.
About thinner wall section (Y portion), cut out test film, and test according to No. 4 test films of the metal material stretching test sheet as JIS Z2201.Wherein, the diameter of parallel portion is made as to 5mm, and gauge length is made as to 4 * A 1/2(sectional area that A is parallel portion).
Recognition methods to recrystallize and non-recrystallization crystal grain describes.
Recrystal grain demonstrates the shape of approximate regular hexagon, if describe, be external in crystal grain circle and in be connected to the circle of crystal grain, the ratio of (the external circular diameter of crystal grain)/(diameter of the inscribed circle of crystal grain) of most of recrystal grain is less than 2.0.Therefore by the ratio of (the external circular diameter of crystal grain)/(diameter of the inscribed circle of crystal grain), be, that more than 2.0 crystal grain is made as non-recrystallization crystal grain.
Measuring method to the average crystallite particle diameter of the recrystal grain group described in this specification sheets and recrystal grain group describes.According to JIS H0501, measure the average crystallite particle diameter of recrystal grain.
Multiplying power is made as to 75 times, in the visual field of 50mm * 70mm, observes metal structure.Wherein, when take 0.15～0.20mm crystal grain thick as border for crystallization particle diameter, be made as 37.5 times.And, when the metal structure in the visual field of its observation is recrystal grain, the set of all recrystal grains in its visual field is made as to the recrystal grain group in its visual field.And if the average crystallite particle diameter of the recrystal grain in the visual field of observing is made as amm, the recrystal grain in its visual field is made as the recrystal grain group that the average crystallite particle diameter of recrystal grain is amm.When the metal structure in the visual field of its observation is non-recrystallization, its visual field is all made as non-recrystallization crystal grain.
Like this, from the whole cross section metal of observing, observe equably 10 visuals field, by each visual field, judge it is recrystal grain or non-recrystallization crystal grain.And, when the visual field of observing is recrystal grain, measure average crystallite particle diameter.Like this, the recrystal grain group shared ratio of the average crystallite particle diameter that calculates recrystal grain in its cross section metal structure according to the observations in 10 visuals field in pre-determined range.
For example be made as follows: in 10 visuals field, 1 visual field is non-recrystallization crystal grain, and 9 visuals field are recrystal grain, in 9 visuals field for recrystal grain, the average crystallite particle diameter in 8 visuals field is 0.050～0.50mm, and the average crystallite particle diameter in 1 visual field is 0.01mm.The shared ratio of recrystal grain group that now the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is 80%, and the shared ratio of non-recrystallization crystal grain is 10%.
In addition, when the visual field of observing be non-recrystallization and recrystallize mix the visual field time, distinguish non-recrystallization crystal grain and recrystal grain (comprising fine crystal grain), and pass through image processing software " WinROOF " by 2 values of recrystallize portion, when its area occupation ratio is judged to be the visual field of non-recrystallization crystal grain less than 20% time, and, when being 80% is judged to be the visual field of recrystal grain when above, be made as in addition and all do not belong to recrystallize portion and non-recrystallization portion.In addition, while being difficult to differentiate recrystallize and non-recrystallization, from EBSP (the Electron Backscatter Diffraction Pattern according to 200 times, Electron Back-Scattered Diffraction figure) crystal grain figure, according to the residual degree of processing strain, recrystallize territory and non-recrystallization territory are distinguished, by image analysis (carrying out 2 values by image processing software " WinROOF "), measured the area occupation ratio in its region.By using EBSP, whether residually in a large number can confirm according to the strain of processing of the present invention.
Carry out as follows the particle size determination of precipitate particle.
By image processing software " WinROOF ", by transmitted electron image 2 values of the TEM of 750,000 times (transmitted electron sensible micro mirror) and extract precipitate, calculate the area average of each precipitate and measure median size.If the wall thickness of test film is made as to h, locates and be made as 2 points from two surperficial 1h/4, and adopt its mean value.And according to the number ratio of the precipitate below the particle size determination 7nm of each precipitate, but it is larger to be judged as error for particle diameter less than the precipitate of 0.7nm, from precipitate particle except (unidentified).
About the mensuration of conductivity, use the electric conductivity measuring apparatus (SIGMATEST D2.068) of Japanese Foerster Co., Ltd. system to measure.Conductivity and electric conductivity are synonym.
About the mensuration of thermal conductivity, the thermal conductivity at measuring 20 ℃ by laser flicker method.
By following creep test, measure creep properties.
Cut out various test films, and carry out according to the stretching test method of the metallic substance of JIS Z2271.In test film, the diameter of parallel portion is made as to 8mm, and gauge length is made as to 40mm.In creep test, for forging, ring forging (test 2), apply 50N/mm 2stress, obtain the total creep deflection under 200 ℃, 1000 hours and do not comprise the total creep deflection of initial deformation.For the ring forging that applies cold working (forging), apply 100N/mm 2stress, obtain the total creep deflection under 200 ℃, 1000 hours and do not comprise the total creep deflection of initial deformation.And the test film after quite testing for soldering also applies 50N/mm 2stress, obtain the total creep deflection under 200 ℃, 1000 hours and do not comprise the total creep deflection of initial deformation.
By the Fig. 6 to Figure 13 that the results are shown in of test 1, by the Figure 14 to Figure 15 that the results are shown in of test 2, and the photo of the metal structure in several tests is shown in to Figure 16.
In addition, in the result table of test 1, the capable result that the X portion of test film is shown of X on hurdle, position, in the capable result that the Y portion of test film is shown of Y.And, in the V on hurdle, position is capable, the project of relevant crystallization particle diameter is recorded to the mensuration mean value in X, Y, Z portion, the project of the project of the particle diameter of relevant precipitate and thermal conductivity, electric conductivity is recorded to the mensuration mean value in X, Y portion, the project of relevant tension test is recorded to the result of the whole test portion that stretches.And, in operation A-0 is capable, record the cooling mechanical properties afterwards in operation A.
Test-results is known as below.
1. as the 1st invention alloy, the ratio that the ratio that recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared and non-recrystallization crystal grain are shared add up to more than 80% copper alloy hot forging, the excellences such as its intensity, endurance, heat conductivity, electrical conductivity.Wherein, the ratio that the ratio that recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.080～0.30mm is shared and non-recrystallization crystal grain are shared add up to more than 80% copper alloy hot forging, they these various characteristicses that comprise creep resistant are excellent.After forging, append the process B of easy continuous heat treatment operation, the operation G that appends 2 forging process, operation E, F that forging temperature is different all demonstrate good various characteristics.And, because being does not utilize solution processing etc. to need the forge hot of the operation of cost, therefore become low cost (with reference to operation A, the B of alloy No.11, C, E, F, G, H etc.).In addition, the intensity of the fast forging of the speed of cooling after forge hot, endurance, heat conductivity, electrical conductivity, creep properties etc. excellent (with reference to operation A, B, C etc.).
2. as the 2nd invention alloy, the ratio that the ratio that recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared and non-recrystallization crystal grain are shared add up to more than 80% copper alloy hot forging, the further grow of its intensity (with reference to operation A, the E of alloy No.21, F, G, H etc.).
3. as the 3rd invention alloy, the ratio that the shared ratio of recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared with non-recrystallization crystal grain add up to more than 80% copper alloy hot forging with the 1st invention alloy time identical, its intensity, endurance, heat conductivity, electrical conductivity etc. excellent (with reference to operation A, B, E, F, G, the H etc. of alloy No.31).
4. if the median size of the precipitate in recrystal grain is 1.3～3.9nm, or that precipitate more than 90% is 0.7～7nm, can there is high endurance, high thermal conductivity, high electrical conductivity, and there is higher creep properties (with reference to operation A, B, C, E, F, the H etc. of alloy No.11) as at 100～200 ℃ of environment for use.
5. if the shared ratio of recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is more than 60%, or the shared ratio of non-recrystallization crystal grain is more than 60%, can there is higher creep properties (with reference to operation F, the G etc. of alloy No.11) as at 100～200 ℃ of environment for use.
6. can access following copper alloy hot forging, its at 825 ℃, heat 300 seconds and cooling after endurance be 125N/mm 2above, the thermal conductivity at described after cooling 20 ℃ is more than 280W/mK, or the electric conductivity at described after cooling 20 ℃ is more than 70%IACS, if described endurance after cooling is made as to L (N/mm 2), the thermal conductivity at described after cooling 20 ℃ is when being made as electric conductivity at M (W/mK), described after cooling 20 ℃ and being made as N (%IACS), (L * M) value is more than 38000, or (L * N) value is more than 9600.And, by implement working modulus after forge hot, be 12% cold working, can make creep properties at endurance and 200 ℃ further excellent (with reference to operation K, the L of alloy No.11, M etc.).
7. if the Heating temperature before forge hot is lower, more than the average crystallite particle diameter of the forging material before forging can not become 0.1mm.If average crystallite particle diameter, not more than 0.1mm, becomes non-recrystallization crystal grain in the thinner wall section of hot forging, even or recrystallize, more than average crystallite particle diameter can not become 0.05mm yet.Even in the heavy section of hot forging, be also difficult to obtain average crystallite particle diameter and be the crystal grain that the less and average crystallite particle diameter of the shared ratio of more than 0.050mm recrystal grain is greater than 0.08mm.In operation E and operation F, the Heating temperature of forging material is identical, more than raw-material average crystallite particle diameter becomes 0.1mm.But due to forging temperature, end temp difference, therefore, in heavy section, although most of recrystallize in two operations, crystallization particle diameter is that the shared ratio of recrystal grain more than 0.08mm there are differences, so in operation F, the particle diameter of precipitate becomes large.Its result, the endurance of operation E, electrical conductivity, heat conductivity are slightly higher.In thinner wall section, owing to becoming non-recrystallization state in operation F, therefore separating out particle diameter is a bit larger tham operation E.In test-results, endurance is slightly higher due to non-recrystallization state for operation F, and heat conductivity/electrical conductivity is slightly lower.If consider just can to know in conjunction with operation A, according to being mainly conceived to which in restriction, forging shape, endurance and the heat conductivity/electrical conductivity of operation/equipment, suitably change hot forging temperature.
8. if that carries out after forge hot separates out after thermal treatment, the speed of cooling till 400 ℃ is made as to 0.8 ℃/min and carries out coolingly, the various characteristics such as intensity, heat-resistant quality is almost unchanged, and electric conductivity improves about 2%IACS.Can think that this is because Co, P etc. are processed afterwards cooling and further fine separated out by delayed heat.Even delayed quench speed, its intensity/conductivity characteristics of comparative example alloy is also the degree improving a little.(with reference to operation A-1)
If with 525≤T+20 * t 1/2≤ 570 separate out thermal treatment, and intensity uprises.If with 560≤T+20 * t 1/2≤ 605 heat-treat, and electricity/heat conductivity uprises.Can think, if improve temperature condition etc., precipitate particle becomes greatly a little, but median size is less than 3.9nm, precipitate more than 90% be 0.7～7nm, so decline a little such as intensity, can separate out more Co and P, so electricity/heat conductivity uprises.(with reference to operation A-1, operation A-2)
If after forge hot and separate out the electric conductivity before thermal treatment: %IACS (45-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]) to (and 55-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[N i]) between, separate out surplus energy, so alloy is reinforced by separating out.Especially, if numerical value be less than (52-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]), or the difference of separating out the electric conductivity after thermal treatment is that 36%IACS is even that more than 40%IACS the characteristic such as intensity, heat-resistant quality further becomes good above.
9. operation I is identical with operation F, although form non-recrystallization tissue, the ratio of non-recrystallization tissue is less than operation F, and forging electric conductivity is afterwards higher, separate out surplus energy less, so intensity is lower, and electricity/heat conductivity is poor.
Can confirm, A compares with operation, and the forging temperature of operation E, F, G, H-1 is lower, but according to the electric conductivity of forging and separate out the solid solution condition that particle diameter still maintains Co and P.
In step H-1, the crystal grain of forging material becomes large, and forging temperature is lower, so most of position of forging becomes non-recrystallization state.And even if forging temperature is lower, the solid solution condition of Co and P is also maintained, by non-recrystallization, organizes and separate out and intensity uprises.And even if be non-recrystallization tissue, the decline of ductility is also less.If suitably select forging condition according to the power of the shape of forging, purposes, swaging machine, can obtain the forging that characteristic is more excellent.
10. the impact of the metal structure after forge hot is narrated.
More than if the heating phase of the forging material of average crystallite particle diameter before forge hot becomes 0.1mm, even after forge hot, more than in heavy section, average crystallite particle diameter also becomes 0.05mm, more than even becoming 0.08mm.Average crystallite particle diameter is larger, and the thermal treatment precipitate particle diameter afterwards of separating out below more diminishes, and can obtain higher endurance, and can obtain higher heat conductivity/electrical conductivity.This be because, strengthen crystallization particle diameter and most of Co and P solid solution by the forging material stage before forging, if therefore separate out thermal treatment, the precipitate of separating out diminishes, and major part can separate out, so heat conductivity/electrical conductivity uprises.In addition, because the average crystallite particle diameter of hot forging is larger, separate out tiny precipitate, so thermotolerance and intensity uprise.And, because average crystallite particle diameter is larger, so the diffusion of Constitution Elements is slow, be difficult to cause the creep strain that relies on the diffusion in atomic level, even if be heated to high temperature, also postpone the solid solution again of precipitate.Thus, even if be equivalent to the thermal treatment of soldering, also can maintain higher intensity, also resistance in creep strain.
11. apply the part of higher working modulus during about forge hot, if hot forging temperature step-down becomes non-recrystallization state.More than average crystallite particle diameter being made as to 0.1mm by the heating phase before forge hot, the size of separating out thermal treatment precipitate afterwards attenuates, and adds the strain being caused by non-recrystallization state, therefore has higher endurance.If the total of the ratio that the ratio that the recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared and non-recrystallization crystal grain are shared accounts for more than 80%, endurance, heat conductivity/electrical conductivity uprise.And, only have average crystallite particle diameter be recrystal grain more than 0.05mm part (being mainly X portion), only have the part (being mainly Y portion) of non-recrystallization crystal grain and the endurance of whole part that they mix, the difference of heat conductivity/electrical conductivity is less.
12. if forging material stages before forging are made as the average crystallite particle diameter of 0.1～5mm, regardless of the beginning temperature of forge hot, end temp (wherein, end temp is more than 700 ℃), in the metal structure forming in forging, average crystallite particle diameter is that any of the tissue of recrystal grain more than 0.05mm or the tissue of non-recrystallization crystal grain all becomes main body, therefore demonstrates good endurance, heat conductivity/fax guiding element.
13. narrate the impact of the speed of cooling after forge hot.If the speed of cooling of 650 ℃ to 550 ℃ is slow after forge hot, separate out thermal treatment endurance, heat conductivity/electrical conductivity step-down afterwards.This can think because separate out thick precipitate when cooling.And it is many that creep strain amount also becomes.
The ring rolling of 14. pairs of tests 2 is made and is narrated.If the Heating temperature of the forging material before forge hot is lower,, along with the decline of hot forging temperature, the solid solution condition of Co and P is unbalance, and it is many that thick precipitate becomes, and therefore separates out thermal treatment endurance afterwards lower, and heat conductivity/electrical conductivity is also poor.Even if suitably heat the forging material before forge hot, if final hot forging temperature is lower, the thick precipitate of Co and P increases, and therefore separates out thermal treatment endurance afterwards lower, and heat conductivity/electrical conductivity is also poor.
If 15. in the salt bath of 825 ℃, 300 seconds dipping ring hot forging heat-treating, more than the average crystallite particle diameter after forge hot increases to 0.08mm, so the crystal grain-growth of precipitate is slow, it is slow that precipitate more or less becomes the solid solution again of large or precipitate.Yet the tiny precipitate of endurance is very abundant owing to contributing to, therefore demonstrate good endurance, heat conductivity/electrical conductivity.In comparative example, the average crystallite particle diameter of original hot forging is less and precipitate is larger, and the solid solution again of precipitate coarsening or precipitate increases, and therefore, endurance, heat conductivity/electrical conductivity are poor.
If ring hot forging involved in the present invention is in the cold working of forge hot after-applied 12%, endurance uprises.This can think because, because the average crystallite particle diameter of hot forging is more than 0.08mm, thus even if be heated to 825 ℃, the processing strain that also can residually import by cold working.Therefore in addition, about creep strain, compare with comparative example, hot forging involved in the present invention is because intensity is higher, and average crystallite particle diameter is larger, so velocity of diffusion is slower, has higher thermotolerance and creep strain amount is less.Apply the hot forging of cold forging because endurance is higher, residual a large amount of processing strains, so creep strain amount is less.
16. if the content of Fe and Ni is outside the compositing range of invention alloy, the formation of precipitate changes, and it is large that precipitate becomes, so endurance, heat conductivity/electrical conductivity are lower, and creep properties is also lower.
17., if the content of Sn is more than the compositing range of invention alloy, heat conductivity/electrical conductivity is lower.And because precipitate is slightly large, so the solution strengthening of Sn cancels out each other, endurance is also slightly low.
18. if the content of Co and P is less than the compositing range of invention alloy, though heat conductivity/electrical conductivity is good, endurance is lower, and creep properties is also poor.
19. even if Co are 0.21～0.44mass% and P is 0.06～0.13mass%, if do not meet the relational expression of 3.1≤([Co]-0.005)/([P]-0.006)≤4.9, residual content Co and P solid solution are in matrix, or the formation of precipitate changes and precipitate becomes large, therefore endurance, heat conductivity/electrical conductivity are lower, and creep properties is also poor.Especially the hot forging of the more test 2 of forging times is due to precipitate coarsening in forge hot, even the median size of precipitate is also larger after thermal treatment, so endurance, heat conductivity/electrical conductivity, creep properties are lower.In addition, if heat-treat at 825 ℃, the precipitate particle of forging is larger, so endurance step-down, poor heat resistance, so creep properties is also lower.
20., if the content of Sn is less than the compositing range of invention alloy, all Co and P can solid solution, therefore residual thick precipitates at short notice.And due to the local coarsening of precipitate in forge hot, it is large that the precipitate after thermal treatment also becomes on the whole, so endurance, heat conductivity/electrical conductivity step-down.
21. from operation A-0 hint, and tensile strength and endurance after forge hot are lower, and ductility value is higher, therefore before separating out processing, easily carries out gagging, can make composite molding higher to tolerance range time.
20. if carry out forge hot, the endurance of C1020, C1220 is significantly low, and thermotolerance is also poor, so creep properties is also lower.
In addition, the invention is not restricted to the formation of above-mentioned embodiment, in the scope that does not change invention aim, can carry out various distortion.
The application advocates right of priority according to Japanese patent application 2010-245994.The full content of its application is by reference to enrolling in the application.
Utilizability in industry
Copper alloy hot forging involved in the present invention is suitable for as radiator element (mixed type power vehicle most, power truck, computer cooling etc.), scatterer, the rotor bar of motor or short-circuited conducting sleeve, power relay, power module components, battery terminal, electric component (pallet, fastening piece, electricity mood distributor, electrode, rly., splicing ear, the various terminals of male terminal etc.), aviation machine/rocket part, welding parts, solar power generation, the purposes of radiator element of power model or nuclear fusion equipment and so on.

Claims (12)

1. an Albatra metal-hot forging, is characterized in that,
The alloy composition of described copper alloy hot forging be the P of Co, 0.06～0.13mass% that contains 0.21～0.44mass%, the Sn of 0.003～0.08mass% and 0.00003～0.0030mass% 0, remainder comprises Cu and inevitable impurity,
The relation between content [Co] mass% of Co and content [P] mass% of P with 3.1≤([Co]-0.005)/([P]-0.006)≤4.9,
In the metal structure of cross section, the adding up to more than 80% of the ratio that the ratio that recrystal grain group that the average crystallite particle diameter of recrystal grain is 0.050～0.50mm is shared and non-recrystallization crystal grain are shared.
2. copper alloy hot forging as claimed in claim 1, is characterized in that,
Further contain the Zn of 0.001～0.3mass%, any more than a kind in the Ag of the Mg of 0.002～0.2mass%, 0.001～0.3mass%.
3. copper alloy hot forging as claimed in claim 1, is characterized in that,
Further contain the Ni of 0.005～0.15mass%, any more than a kind in the Fe of 0.003～0.10mass%,
The relation between content [Fe] mass% of content [Ni] mass%, Fe of content [Co] mass%, the Ni of Co and content [P] mass% of P with 3.1≤([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006)≤4.9 and 0.010≤2 * [Ni]+3 * [Fe]≤0.75 * [Co].
4. copper alloy hot forging as claimed in claim 2, is characterized in that,
Further contain the Ni of 0.005～0.15mass%, any more than a kind in the Fe of 0.003～0.10mass%,
The relation between content [Fe] mass% of content [Ni] mass%, Fe of content [Co] mass%, the Ni of Co and content [P] mass% of P with 3.1≤([Co]+0.9 * [Ni]+0.8 * [Fe]-0.005)/([P]-0.006)≤4.9 and 0.010≤2 * [Ni]+3 * [Fe]≤0.75 * [Co].
5. the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
Endurance is 230N/mm 2above,
Thermal conductivity at 20 ℃ is more than 300W/mK, or the electric conductivity at 20 ℃ is more than 75%IACS,
Described endurance is made as to L (N/mm 2), described thermal conductivity is when being made as M (W/mK), described electric conductivity and being made as N (%IACS), the value of (L * M) is more than 77000, or the value of (L * N) is more than 19000.
6. the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
The median size of the precipitate in described recrystal grain is 1.3～3.9nm, or that precipitate more than 90% is 0.7～7nm.
7. the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
The shared ratio of described recrystal grain group that the average crystallite particle diameter of described recrystal grain is 0.050～0.50mm is more than 60%, or the shared ratio of described non-recrystallization crystal grain is more than 60%.
8. the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
At 825 ℃, heated for 300 seconds, cooling endurance is afterwards 125N/mm 2above,
Thermal conductivity at described after cooling 20 ℃ is more than 280W/mK, or the electric conductivity at described after cooling 20 ℃ is more than 70%IACS,
Described cooling endurance is afterwards made as to L (N/mm 2), the thermal conductivity at described after cooling 20 ℃ is when being made as electric conductivity at M (W/mK), described after cooling 20 ℃ and being made as N (%IACS), the value of (L * M) is more than 38000, or the value of (L * N) is more than 9600.
9. a manufacture method for the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
The Heating temperature being subjected to before the forge hot of forging material of forge hot is 925～1025 ℃, and average crystallite particle diameter when the described heating of described forging material finishes is 0.10～5.0mm.
10. a manufacture method for the copper alloy hot forging as described in any one in claim 1 to 4, is characterized in that,
With 700 ℃ of above enforcements, be subjected at least 1 forge hot of the forging material of forge hot,
After described forge hot, with 12 ℃/sec of above speed of cooling, described forging material is cooled to below 400 ℃, or with 12 ℃/sec of above speed of cooling, the temperature province of 650 ℃ to 550 ℃, carry out cooling,
Described cooling after, after described forging material is carried out to cold working or do not carry out cold working, heat-treat, this heat treated condition is for as follows: the thermal treatment temp of 450～600 ℃ and hold-time are 0.2～10 hour, if described thermal treatment temp is made as to T ℃ and the described hold-time is made as to t hour, meet 520≤T+20 * t 1/2≤ 615 relation.
11. 1 Albatra metal-hot forgings, its manufacture method by copper alloy hot forging as claimed in claim 10 is manufactured, it is characterized in that,
If the electric conductivity after described forge hot and before described thermal treatment is made as to X (%IACS), between content [Mg] mass% of content [Sn] mass%, Mg of content [Fe] mass%, the Sn of content [Co] mass%, the Fe of content [P] mass%, the Co of X, P and content [Ni] mass% of Ni, have (45-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni])≤X≤(55-25[P]-20[Co]-10[Fe]-5[Sn]-3[Mg]-2[Ni]) relation.
The manufacture method of 12. 1 kinds of copper alloy hot forgings as described in any one in claim 1 to 4, is characterized in that,
With 700 ℃ of above enforcements, be subjected at least 1 forge hot of the forging material of forge hot,
After described forge hot, with 12 ℃/sec of above speed of cooling, the temperature province of 650 ℃ to 550 ℃, described forging material is carried out coolingly, describedly the temperature province of 400～540 ℃, keep 10～200 minutes after cooling.
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